Novel cyclohexanols and their use in perfume compositions

ABSTRACT

The present invention is directed to novel fragrance compounds and their unexpected advantageous use in improving, enhancing or modifying a fragrance formulation through the addition of an olfactory acceptable amount of the compounds, wherein the compounds are represented by the following formula: 
     
       
         
         
             
             
         
       
         
         
           
             an isomer or a mixture of isomers thereof, 
             wherein one of R and R′ represents hydrogen with the other representing a C 1 -C 6  linear, branched, or cyclic alkyl, alkenyl, alkynyl or aromatic group; and 
             one of the dashed lines represents a carbon-carbon single bond with the other representing a carbon-carbon double bond.

STATUS OF RELATED APPLICATIONS

This application is a divisional of U.S. Ser. No. 14/336,036, filed Jul.21, 2014, now allowed, the content hereby incorporated by reference asif set forth in its entirety.

FIELD OF THE INVENTION

The present invention relates to new chemical entities and theincorporation and use of the new chemical entities as fragrancematerials.

BACKGROUND OF THE INVENTION

There is an ongoing need in the fragrance industry to provide newchemicals to give perfumers and other persons the ability to create newfragrances for perfumes, colognes and personal care products. Those withskill in the art appreciate how small differences in chemical structurescan result in unexpected and significant differences in odor, notes andcharacteristics of molecules. These variations allow perfumers and otherpersons to apply new compounds in creating new fragrances.

SUMMARY OF THE INVENTION

The present invention provides novel chemicals and their unexpectedadvantageous use in improving, enhancing or modifying the fragrance ofperfumes, colognes, toilet waters, cosmetic products, personal careproducts, fabric care products, cleaning products, air fresheners, andthe like.

One embodiment of the present invention is directed to novelcyclohexanol compounds represented by the following formula:

-   -   isomers or mixtures of isomers thereof,    -   wherein one of R and R′ represents hydrogen with the other        representing a C₁-C₆ linear, branched, or cyclic alkyl, alkenyl,        alkynyl or aromatic group; and    -   one of the dashed lines represents a carbon-carbon single bond        with the other representing a carbon-carbon double bond.

Another embodiment of the present invention is directed to the use ofthe compounds provided above as fragrance materials in perfumes,colognes, toilet waters, personal products, fabric care products, andthe like.

Another embodiment of the present invention is directed to a fragrancecomposition comprising the compounds provided above.

Another embodiment of the present invention is directed to a fragranceproduct comprising the compounds provided above.

Another embodiment of the present invention is directed to a method ofimproving, enhancing or modifying a fragrance formulation byincorporating an olfactory acceptable amount of the compounds providedabove.

These and other embodiments of the present invention will be apparent byreading the following specification.

DETAILED DESCRIPTION OF THE INVENTION

The compounds of the present invention may also be represented byethylidene-substituted cyclohexanols of Formula II and vinyl-substitutedcyclohexanols of Formula III in the following:

-   -   isomers or mixtures of isomers thereof,    -   wherein R and R′ are defined as above.

The compounds of the present invention may be further represented bycyclohexanols of Formula IV in the following:

-   -   isomers or mixtures of isomers thereof,    -   wherein one of R¹ and R² represents hydrogen with the other        representing a C₁-C₆ linear, branched or cyclic alkyl group; and    -   one of the dashed lines represents a carbon-carbon single bond        with the other representing a carbon-carbon double bond.

The cyclohexanol compounds of Formula II, III and IV may be furtherrepresented by Formula V and Formula VI in the following:

-   -   isomers or mixtures of isomers thereof,    -   wherein one of R¹ and R² are defined as above.

The novel cyclohexanols of the present invention are illustrated, forexample, by following examples.

(E)-4-Ethylidene-2-methoxy-cyclohexanol:

(Z)-4-Ethylidene-2-methoxy-cyclohexanol:

(E)-5-Ethylidene-2-methoxy-cyclohexanol:

(Z)-5-Ethylidene-2-methoxy-cyclohexanol:

(E)-4-Ethylidene-2-ethoxy-cyclohexanol:

(Z)-4-Ethylidene-2-ethoxy-cyclohexanol:

(E)-5-Ethylidene-2-ethoxy-cyclohexanol:

(Z)-5-Ethylidene-2-ethoxy-cyclohexanol:

(E)-4-Ethylidene-2-vinyloxy-cyclohexanol:

(Z)-4-Ethylidene-2-vinyloxy-cyclohexanol:

(E)-5-Ethylidene-2-vinyloxy-cyclohexanol:

(Z)-5-Ethylidene-2-vinyloxy-cyclohexanol:

(E)-4-Ethylidene-2-ethynyloxy-cyclohexanol:

(Z)-4-Ethylidene-2-ethynyloxy-cyclohexanol:

(E)-5-Ethylidene-2-ethynyloxy-cyclohexanol:

(Z)-5-Ethylidene-2-ethynyloxy-cyclohexanol:

(E)-4-Ethylidene-2-propoxy-cyclohexanol:

(Z)-4-Ethylidene-2-propoxy-cyclohexanol:

(E)-5-Ethylidene-2-propoxy-cyclohexanol:

(Z)-5-Ethylidene-2-propoxy-cyclohexanol:

(E)-4-Ethylidene-2-isopropoxy-cyclohexanol:

(Z)-4-Ethylidene-2-isopropoxy-cyclohexanol:

(E)-5-Ethylidene-2-isopropoxy-cyclohexanol:

(Z)-5-Ethylidene-2-isopropoxy-cyclohexanol:

2-Methoxy-4-vinyl-cyclohexanol:

2-Methoxy-5-vinyl-cyclohexanol:

2-Ethoxy-4-vinyl-cyclohexanol:

2-Ethoxy-5-vinyl-cyclohexanol:

2-Propoxy-4-vinyl-cyclohexanol:

2-Propoxy-5-vinyl-cyclohexanol:

2-Allyloxy-4-vinyl-cyclohexanol:

2-Allyloxy-5 -vinyl-cyclohexanol:

2-Prop-2-ynyloxy-4-vinyl-cyclohexanol:

2-Prop-2-ynyloxy-5 -vinyl-cyclohexanol:

2-Isopropoxy-4-vinyl-cyclohexanol:

2-Isopropoxy-5-vinyl-cyclohexanol:

2-Butoxy-4-vinyl-cyclohexanol:

2-Butoxy-5 -vinyl-cyclohexanol:

2-Isobutoxy-4-vinyl-cyclohexanol:

2-Isobutoxy-5 -vinyl-cyclohexanol:

The compounds of the present invention were prepared with3-vinyl-7-oxa-bicyclo[4.1.0]heptane according to the following reactionscheme, the details of which are specified in the Examples. Materialsand catalysts were purchased from Aldrich Chemical Company unless notedotherwise.

-   -   wherein RhCl₃ represents Rhodium (III) chloride; and    -   R and R′ are defined as above.

Those with skill in the art will recognize that some of the compounds ofthe present invention have a number of chiral centers, thereby providingnumerous isomers of the claimed compounds. It is intended herein thatthe compounds described herein include isomeric mixtures of suchcompounds, as well as those isomers that may be separated usingtechniques known to those having skill in the art. Suitable techniquesinclude chromatography such as high performance liquid chromatography,referred to as HPLC, particularly silica gel chromatograph, and gaschromatography trapping known as GC trapping. Yet, commercial versionsof such products are mostly offered as mixtures.

The compounds of the present invention, for example, possess strong andcomplex sweet, spicy, woody and vanilla notes.

The use of the compounds of the present invention is widely applicablein current perfumery products, including the preparation of perfumes andcolognes, the perfuming of personal care products such as soaps, showergels, and hair care products, fabric care products as well as airfresheners and cosmetic preparations. These compounds can also be usedto perfume cleaning agents, such as, but not limited to detergents,dishwashing materials, scrubbing compositions, window cleaners and thelike. In these preparations, the compounds of the present invention canbe used alone or in combination with other perfuming compositions,solvents, adjuvants and the like. The nature and variety of the otheringredients that can also be employed are known to those with skill inthe art.

Many types of fragrances can be employed in the present invention, theonly limitation being the compatibility with the other components beingemployed. Suitable fragrances include but are not limited to fruits suchas almond, apple, cherry, grape, pear, pineapple, orange, strawberry,raspberry; musk; and flower scents such as lavender-like, rose-like,iris-like, carnation-like. Other pleasant scents include herbal andwoodland scents derived from pine, spruce and other forest smells.Fragrances may also be derived from various oils, such as essentialoils, or from plant materials such as peppermint, spearmint and thelike.

A list of suitable fragrances is provided in U.S. Pat. No. 4,534,891,the contents of which are incorporated by reference as if set forth inits entirety. Another source of suitable fragrances is found inPerfumes, Cosmetics and Soaps, Second Edition, edited by W. A. Poucher,1959. Among the fragrances provided in this treatise are acacia, cassie,chypre, cyclamen, fern, gardenia, hawthorn, heliotrope, honeysuckle,hyacinth, jasmine, lilac, lily, magnolia, mimosa, narcissus, freshly-cuthay, orange blossom, orchid, reseda, sweet pea, trefle, tuberose,vanilla, violet, wallflower, and the like.

The term “improving” in the phrase “improving, enhancing or modifying afragrance formulation” is understood to mean raising the fragranceformulation to a more desirable character. The term “enhancing” isunderstood to mean making the fragrance formulation greater ineffectiveness or providing the fragrance formulation with an improvedcharacter. The term “modifying” is understood to mean providing thefragrance formulation with a change in character.

The terms “fragrance formulation”, “fragrance composition”, and “perfumecomposition” are understood to mean the same and refer to a formulationthat is intended for providing a fragrance character to a perfume, acologne, toilet water, a personal product, a fabric care product, andthe like. The fragrance formulation of the present invention is acomposition comprising a compound of the present invention.

Olfactory acceptable amount is understood to mean the amount of acompound in a perfume composition. The compound will contribute itsparticular olfactory characteristics, but the olfactory effect of theperfume composition will be the sum of the effects of each of theperfumes or fragrance ingredients. Thus the compounds of the inventioncan be used to alter the aroma characteristics of a perfume composition,or by modifying the olfactory reaction contributed by another ingredientin the composition. The amount will vary depending on many factorsincluding other ingredients, their relative amounts and the effect thatis desired.

The amount of the compounds of the present invention employed in afragrance formulation varies from about 0.005 to about 70 weightpercent, preferably from 0.005 to about 50 weight percent, morepreferably from about 0.5 to about 25 weight percent, and even morepreferably from about 1 to about 10 weight percent. Those with skill inthe art will be able to employ the desired amount to provide desiredfragrance effect and intensity. In addition to the compounds of thepresent invention, other materials can also be used in conjunction withthe fragrance formulation. Well known materials such as surfactants,emulsifiers, polymers to encapsulate the fragrance can also be employedwithout departing from the scope of the present invention.

The following are provided as specific embodiments of the presentinvention. Other modifications of this invention will be readilyapparent to those skilled in the art. Such modifications are understoodto be within the scope of this invention. The chemical materials used inthe preparation of the compounds of the present invention arecommercially available from Aldrich Chemical Company. As used herein allpercentages are weight percent unless otherwise noted, ppm is understoodto stand for parts per million, mol is understood to be mole, mmol isunderstood to be millimole, L is understood to be liter, mL isunderstood to be milliliter, Kg is understood to be kilogram and g begram, psi is understood to be pound-force per square inch, and mmHg isunderstood to be millimeters (mm) of mercury (Hg). IFF as used in theexamples is understood to mean International Flavors & Fragrances Inc.,New York, N.Y., USA.

EXAMPLE I

Preparation of 2-Propoxy-4-vinyl-cyclohexanol (Structure 29) and2-Propoxy-5-vinyl-cyclohexanol (Structure 30):

A 5-L, 4-neck round bottom flask was fitted with a temperature probe, aglass stir shaft, a water condenser and an addition funnel Propanol(CH3CH2CH2OH) (1.4 Kg) and Amberlyst® 15 (15 g) were charged into theflask and brought to reflux. 3-Vinyl-7-oxa-bicyclo[4.1.0]heptane (476 g,3.8 mol) was fed in over 1 hour. The reaction was aged for additional 6hours and then cooled to room temperature. The reaction mixture wasdecanted to provide a mixture of 2-propoxy-4-vinyl-cyclohexanol(Structure 29) and 2-propoxy-5-vinyl-cyclohexanol (Structure 30) (1:1)(699 g).

¹H NMR (CDCl₃, 400 MHz): 5.78-5.90 (m, 1H), 4.94-5.15 (m, 2H), 3.06-3.79(m, 4H), 2.46-2.58 (m, 1H), 2.34-2.45 (m, 1H), 1.80-2.05 (m, 2H),1.42-1.72 (m, 6H), 0.93 (t, J=7.4 Hz, 3H)

The isomeric mixture Structure 29 and 30 was described as having sweet,spicy and vanilla notes.

EXAMPLE II

Preparation of (E)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 17),(Z)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 18),(E)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 19) and(Z)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 20):

The mixture of 2-propoxy-4-vinyl-cyclohexanol (Structure 29) and2-propoxy-5-vinyl-cyclohexanol (Structure 30) (699 g) (prepared as abovein Example I) and RhCl₃ (2.0 g, 9.6 mmol) were combined in a fresh 5-L,4-neck round bottom flask fitted with a temperature probe, a glass stirshaft and a Dean-Stark trap. The reaction mixture was heated to reflux.About 600 mL propanol was removed via the Dean-Stark trap during thereaction. The reaction mixture was aged at reflux for additional 5hours. Gas chromatography (GC) analysis was used to monitor thecompletion of the reaction. The reaction mixture was then cooled.Further distillation at a vapor temperature of 123° C. with a pressureof 2 mmHg provided the mixture of(E)-4-ethylidene-2-propoxy-cyclohexanol (Structure 17),(Z)-4-ethylidene-2-propoxy-cyclohexanol (Structure 18),(E)-5-ethylidene-2-propoxy-cyclohexanol (Structure 19) and(Z)-5-ethylidene-2-propoxy-cyclohexanol (Structure 20) (Structure17:Structure 18:Structure 19:Structure 20=about 0.74:0.83:0.95:1.0) (575g, 79% yield).

The mixture of (E)-4-ethylidene-2-propoxy-cyclohexanol (Structure 17),(Z)-4-ethylidene-2-propoxy-cyclohexanol (Structure 18),(E)-5-ethylidene-2-propoxy-cyclohexanol (Structure 19) and(Z)-5-ethylidene-2-propoxy-cyclohexanol has the following NMR spectralcharacteristics:

¹H NMR (CDCl₃, 500 MHz): 5.14-5.34 ppm (m, 1H), 1.66-3.68 ppm (m, 10H),1.52-1.66 ppm (m, 5H), 1.09-1.34 ppm (m, 1H), 0.88-1.02 ppm (m, 3H)

The isomeric mixture Structure 17, 18, 19 and 20 was described as havingparticularly desirable, strong and complex sweet, spicy, woody andvanilla notes.

(E)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 17) has the followingNMR spectral characteristics:

¹H NMR (CDCl3, 500 MHz): 5.22-5.30 ppm (m, 1H), 3.57-3.64 ppm (m, 1H),3.51-3.57 ppm (m, 1H), 3.30-3.40 ppm (m, 2H), 2.92-3.03 ppm (m, 1H),2.67 ppm (br, 1H), 2.47-2.64 ppm (m, 2H), 2.02-2.10 ppm (m, 1H),1.86-1.94 ppm (m, 1H), 1.66-1.78 ppm (m, 1H), 1.56-1.66 ppm (m, 5H),1.19-1.29 (m, 1H), 0.94 (t, 3H, J=7.41 Hz)

(E)-4-Ethylidene-2-propoxy-cyclohexanol was described as having spicy,clove-leaf, floral and medicinal notes.

(Z)-4-Ethylidene-2-propoxy-cyclohexanol (Structure 18) has the followingNMR spectral characteristics:

¹H NMR (CDCl₃, 500 MHz): 5.25-5.32 ppm (m, 1H), 3.62-3.70 ppm (m, 1H),3.50-3.62 ppm (m, 1H), 3.31-3.43 ppm (m, 1H), 2.95-3.03 ppm (m, 2H),2.66 ppm (br, 1H), 2.13-2.20 ppm (m, 1H), 1.98-2.08 ppm (m, 2H),1.55-1.66 ppm (m, 6H), 1.23-1.34 ppm (m, 1H), 0.96 ppm(t, 3H, J=7.41 Hz)

(Z)-4-Ethylidene-2-propoxy-cyclohexanol was described as having spicy,clove-leaf and medicinal notes.

(E)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 19) has the followingNMR spectral characteristics:

¹H NMR (CDCl₃, 500 MHz): 5.23-5.30 ppm (m, 1H), 3.56-3.64 ppm (m, 1H),3.41-3.47 ppm (m, 1H), 3.33-3.39 ppm (m, 1H), 3.13-3.20 ppm (m, 1H),2.58 ppm (br, 1H), 2.48-2.60 ppm (m, 2H), 2.02-2.10 ppm (m, 2H),1.67-1.78 ppm (m, 1H), 1.55-1.67 ppm (m, 5H), 1.11-1.21 ppm (m, 1H),0.94 ppm (t, 3H, J=7.41 Hz)

(E)-5-Ethylidene-2-propoxy-cyclohexanol was described as havingbalsamic, sweet, spicy and vanilla notes.

(Z)-5-Ethylidene-2-propoxy-cyclohexanol (Structure 20) has the followingNMR spectral characteristics:

¹H NMR (CDCl₃, 500 MHz): 5.25-5.36 ppm (m, 1H), 3.57-3.64 ppm (m, 1H),3.32-3.43 ppm (m, 2H), 3.13-3.20 ppm (m, 1H), 2.86-2.93 ppm (m, 1H),2.66 ppm (br, 1H), 2.17-2.23 ppm (m, 1H), 1.96-2.10 ppm (m, 2H),1.76-1.84 ppm (m, 1H), 1.56-1.67 (m, 5H), 1.13-1.24 ppm (m, 1H), 0.94ppm (t, 3H, J=7.41 Hz)

(Z)-5-Ethylidene-2-propoxy-cyclohexanol was described as having spicy,clove-leaf, medicinal and slight cooling herbal notes.

EXAMPLE III

Following cyclohexanols were similarly prepared.

(E)-4-Ethylidene-2-methoxy-cyclohexanol (Structure 1),(Z)-4-Ethylidene-2-methoxy-cyclohexanol (Structure 2),(E)-5-Ethylidene-2-methoxy-cyclohexanol (Structure 3) and(Z)-5-Ethylidene-2-methoxy-cyclohexanol (Structure 4):

¹H NMR (CDCl₃, 400 MHz): 5.15-5.43 (m, 1H), 3.32-3.62 (m, 4H), 1.94-3.14(m, 6H), 1.67-1.94 (m, 1H), 1.48-1.67 (m, 3H), 1.08-1.37 (m, 1H)

The isomeric mixture of Structure 1, 2, 3 and 4 was described as havingbalsamic, sweet, spicy, fruity, fresh and minty notes.

(E)-4-Ethylidene-2-ethoxy-cyclohexanol (Structure 5),(Z)-4-Ethylidene-2-ethoxy-cyclohexanol (Structure 6),(E)-5-Ethylidene-2-ethoxy-cyclohexanol (Structure 7) and(Z)-5-Ethylidene-2-ethoxy-cyclohexanol (Structure 8):

¹H NMR (CDCl₃, 400 MHz): 5.16-5.38 (m, 1H), 3.32-3.85 (m, 3H), 2.12-3.25(m, 4H), 1.84-2.11 m, 2H), 1.64-1.84 (m, 1H), 1.48-1.64 (m, 3H),1.04-1.34 (m, 4H)

The isomeric mixture of Structure 5, 6, 7 and 8 was described as havingstrong and complex sweet, spicy, fruity, woody, clove-leaf, floral,green, smoky and leathery notes.

(E)-4-Ethylidene-2-isopropoxy-cyclohexanol (Structure 21),(Z)-4-Ethylidene-2-isopropoxy-cyclohexanol (Structure 22),(E)-5-Ethylidene-2-isopropoxy-cyclohexanol (Structure 23) and(Z)-5-Ethylidene-2-isopropoxy-cyclohexanol (Structure 24):

¹H NMR (CDCl₃, 400 MHz): 5.18-5.33 (m, 1H), 3.65-3.85 (m, 1H), 2.96-3.57(m, 2H), 1.87-2.95 (m, 5H), 1.63-1.87 (m, 1H), 1.50-1.63 (m, 3H),1.07-1.36 (m, 7H)

The isomeric mixture of Structure 21, 22, 23 and 24 was described ashaving sweet, spicy, woody and vanilla notes.

2-Methoxy-4-vinyl-cyclohexanol (Structure 25) and2-Methoxy-5-vinyl-cyclohexanol (Structure 26):

¹H NMR (CDCl₃, 500 MHz): 5.73-5.92 (m, 1H), 4.94-5.14 (m, 2H), 3.67-3.83(m, 1H), 3.38 (s, 3H), 3.01-3.29 (m, 1H), 2.37-2.60 (m, 2H), 1.79-2.03(m, 2H), 1.44-1.68 (m, 4H)

The isomeric mixture of Structure 25 and 26 was described as havingfruity, vanilla and green notes.

2-Ethoxy-4-vinyl-cyclohexanol (Structure 27) and2-Ethoxy-5-vinyl-cyclohexanol (Structure 28):

¹H NMR (CDCl₃, 500 MHz): 5.74-5.96 (m, 1H), 4.95-5.17 (m, 2H), 3.07-3.77(m, 4H), 2.47-2.57 (m, 1H), 2.18-2.45 (br, 1H), 1.78-2.06 (m, 2H),1.42-1.72 (m, 4H), 1.20 (t, J=6.9 Hz, 3H)

The isomeric mixture of Structure 27 and 28 was described as havingspicy and vanilla notes.

2-Isopropoxy-4-vinyl-cyclohexanol (Structure 35) and2-Isopropoxy-5-vinyl-cyclohexanol (Structure 36):

¹H NMR (CDCl₃, 400 MHz): 5.68-5.95 (m, 1H), 4.89-5.16 (m, 2H), 3.16-3.83(m, 3H), 2.70-2.86 (m, 1H), 2.41-2.61 (m, 1H), 1.73-1.98 (m, 2H),1.43-1.73 (m, 4H), 1.10-1.22 (m, 6H)

The isomeric mixture of Structure 35 and 36 was described as having aspicy note.

2-Butoxy-4-vinyl-cyclohexanol (Structure 37)2-Butoxy-5-vinyl-cyclohexanol (Structure 38):

¹H NMR (CDCl₃, 400 MHz): 5.68-5.95 (m, 1H), 4.91-5.14 (m, 2H), 3.04-3.80(m, 4H), 2.41-2.66 (m, 2H), 1.79-2.05 (m, 2H), 1.44-1.73 (m, 6H),1.31-1.44 (m, 2H), 0.92 (t, J=7.3 Hz, 3H)

The isomeric mixture of Structure 37 and 38 was described as havingsweet and spicy notes.

2-Isobutoxy-4-vinyl-cyclohexanol (Structure 39) and2-Isobutoxy-5-vinyl-cyclohexanol (Structure 40):

¹H NMR (CDCl₃, 400 MHz): 5.72-5.98 (m, 1H), 4.86-5.14 (m, 2H), 3.56-3.83(m, 1H), 3.06-3.40 m, 3H), 2.41-2.63 (m, 2H), 1.74-2.00 (m, 3H),1.44-1.73 (m, 4H), 0.85-0.95 (m, 6H)

The isomeric mixture of Structure 39 and 40 was described as havingonion- and garlic-like notes.

EXAMPLE IV

Additional hydrogenated cyclohexanols were prepared via thehydrogenation of the corresponding cyclohexanols prepared in the above.

4-Ethyl-2-methoxy-cyclohexanol (Structure 41) and5-Ethyl-2-methoxy-cyclohexanol (Structure 42):

¹H NMR (CDCl₃, 500 MHz): 3.57-3.74 (m, 1H), 3.38 (s, 3H), 3.02-3.21 (m,1H), 2.32 (br, s, 1H), 1.74-1.89 (m, 2H), 1.59-1.68 (m, 1H), 1.39-1.55(m, 4H), 1.26-1.35 (m, 2H), 0.87-0.92 (m, 3H)

The isomeric mixture of Structure 41 and 42 was described as havingspicy and vanilla but phenolic notes.

4-Ethyl-2-ethoxy-cyclohexanol (Structure 43) and5-Ethyl-2-Ethoxy-cyclohexanol (Structure 44):

¹H NMR (CDCl₃, 500 MHz): 2.96-3.78 (m, 4H), 2.50 (br, s, 1H), 1.96-2.13(m, 1H), 1.57-1.88 (m, 2H), 1.36-1.57 (m, 2H), 1.08-1.36 (m, 6H),0.77-1.04 (m, 4H)

The isomeric mixture of Structure 43 and 44 was described as havingearthy, woody and green but phenolic notes.

4-Ethyl-2-propoxy-cyclohexanol (Structure 45) and5-Ethyl-2-propoxy-cyclohexanol (Structure 46):

¹H NMR (CDCl₃, 400 MHz): 2.91-3.92 (m, 5H), 1.06-2.16 (m, 11H),0.72-1.03 (m, 6H)

The isomeric mixture of Structure 45 and 46 was described as havingspicy and vanilla but phenolic notes.

4-Ethyl-2-isobutoxy-cyclohexanol (Structure 47) and5-Ethyl-2-isobutoxy-cyclohexanol (Structure 48):

¹H NMR (CDCl₃, 400 MHz): 2.58-3.76 (m, 5H), 1.00-2.14 (m, 10H),0.77-1.00 (m, 9H)

The isomeric mixture of Structure 47 and 48 was described as havingspicy and woody notes with bacon character.

Accordingly, the novel cyclohexanols represented by Formula I-VI possessunexpected superior and desirable effect when compared to theircorresponding hydrogenated compounds.

What is claimed is:
 1. A fragrance formulation containing an olfactoryacceptable amount of a compound of formula:

an isomer or a mixture of isomers thereof, wherein one of R and R′represents hydrogen with the other representing a C₁-C₆ linear,branched, or cyclic alkyl, alkenyl, alkynyl or aromatic group; and oneof the dashed lines represents a carbon-carbon single bond with theother representing a carbon-carbon double bond.
 2. The fragranceformulation of claim 1, wherein in the compound is a compound offormula:

an isomer or a mixture of isomers thereof, wherein one of R¹ and R²represents hydrogen with the other representing a C₁-C₆ linear, branchedor cyclic alkyl group; and one of the dashed lines represents acarbon-carbon single bond with the other representing a carbon-carbondouble bond.
 3. The fragrance formulation of claim 1, wherein thecompound is a compound of formula:

an isomer or a mixture of isomers thereof, wherein one of R¹ and R²represents hydrogen with the other representing a C₁-C₆ linear, branchedor cyclic alkyl group.
 4. The fragrance formulation of claim 3, whereinthe compound is selected from the group consisting of:(E)-4-Ethylidene-2-methoxy-cyclohexanol;(Z)-4-Ethylidene-2-methoxy-cyclohexanol;(E)-5-Ethylidene-2-methoxy-cyclohexanol;(Z)-5-Ethylidene-2-methoxy-cyclohexanol;(E)-4-Ethylidene-2-ethoxy-cyclohexanol;(Z)-4-Ethylidene-2-ethoxy-cyclohexanol;(E)-5-Ethylidene-2-ethoxy-cyclohexanol;(Z)-5-Ethylidene-2-ethoxy-cyclohexanol;(E)-4-Ethylidene-2-propoxy-cyclohexanol;(Z)-4-Ethylidene-2-propoxy-cyclohexanol;(E)-5-Ethylidene-2-propoxy-cyclohexanol;(Z)-5-Ethylidene-2-propoxy-cyclohexanol;(E)-4-Ethylidene-2-isopropoxy-cyclohexanol;(Z)-4-Ethylidene-2-isopropoxy-cyclohexanol;(E)-5-Ethylidene-2-isopropoxy-cyclohexanol;(Z)-5-Ethylidene-2-isopropoxy-cyclohexanol; and a mixture thereof. 5.The fragrance formulation of claim 1 further comprising a productselected from the group consisting of a perfume, a cologne, toiletwater, a cosmetic product, a personal care product, a fabric careproduct, a cleaning product and an air freshener.
 6. The fragranceformulation of claim 5, wherein the cleaning product is selected fromthe group consisting of a detergent, a dishwashing composition, ascrubbing compound, and a window cleaner. The fragrance formulation ofclaim 1, wherein the olfactory acceptable amount is from about 0.005 toabout 50 weight percent of the fragrance formulation.
 8. The fragranceformulation of claim 1, wherein the olfactory acceptable amount is fromabout 0.5 to about 25 weight percent of the fragrance formulation. 9.The fragrance formulation of claim 1, wherein the olfactory acceptableamount is from about 1 to about 10 weight percent of the fragranceformulation.